JP2005054306A - Wrinkle remover composition of fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for removing wrinkles of a fiber product, capable of being carried out in ordinary homes without requiring ironing. <P>SOLUTION: The fiber product is heat-treated by using a wrinkle remover composition containing (a) a (poly)glycerol-modified silicone and (b) an organic compound having 30-100°C melting point by a rotary heated dryer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a wrinkle removing composition for textiles, a wrinkle removing material, and a method for removing wrinkles. In particular, the present invention relates to a technique suitable for processing a textile product using a rotary dryer.

  Wrinkles are formed in clothes such as shirts and polo shirts through washing / rinsing / dehydration / drying, and wrinkles are formed to such an extent that clothes mainly composed of cellulosic fibers such as cotton cannot be worn without ironing. In recent years, shirts that have been subjected to form stabilization processing have become widespread, but these have also been reduced in effectiveness as they are repeatedly worn / washed, and ironing has not been eliminated at all. However, since ironing is one of the most labor-intensive tasks, there is an eager desire for a method that can remove wrinkles as easily as possible without ironing.

  Much research has been done on industrial and household applications on how to remove wrinkles from clothing. As a method developed for industrial use, Patent Documents 1 to 3 disclose a method for producing a cellulose fiber having a wrinkle-proof effect and a shrink-proof effect, in which a fiber is impregnated with a treatment agent containing polycarboxylic acid and heat-treated. Has been. Patent Documents 4 to 8 disclose fiber treatment agents using specific polyorganosiloxane compounds. However, these techniques have been developed for industrial use and do not disclose any method for easily removing wrinkles in a general household.

  As a method for easily removing wrinkles at home, Patent Documents 9 to 10 disclose a wrinkle removing aqueous composition that does not require an iron for spraying. Patent Document 11 discloses a technique of a cleaning agent that suppresses wrinkle formation using a nonionic surfactant such as polyhydroxy fatty acid amide as a cleaning component. However, the garments covered by these technologies are wrinkles for wearing wool products such as suits and slacks. Although these garments are effective to some extent, they have a satisfactory effect on the wrinkles of cotton products. is not.

On the other hand, polyglycerol modified silicone is already known. Patent Document 12 discloses a method for producing a silicone compound having a polyglycerol group using an oxyalkylene group as a linking group, and Patent Document 13 discloses a method for producing a silicone compound having a polyglycerol group using an ester group as a linking group. Is disclosed. However, the above prior art is applied to cosmetics and hair cleaning agents, and does not suggest any effect when used in textile products. Moreover, although the application to a fiber processing agent is suggested by patent document 12, it does not suggest at all that it has a high effect in the wrinkle removal of a textile product by performing a specific processing method.
JP-A-7-243176 JP-A-8-27666 JP-A-8-13334 JP-A-7-70937 JP-A-9-228255 JP-A-9-217282 JP-A-10-96173 Japanese Patent Laid-Open No. 10-195781 Japanese Patent Laid-Open No. 10-25660 Japanese Patent Laid-Open No. 10-46471 JP 2001-526741 A JP-A-57-149290 JP-A-9-278892

  Accordingly, an object of the present invention is to provide a method for removing wrinkles of a textile product that does not require ironing and can be easily performed in a general household, a wrinkle removing composition that can impart the effect to the textile product, and a wrinkle removing material. is there.

  The present invention comprises a rotary type containing (a) (poly) glycerol-modified silicone (hereinafter referred to as component (a)) and (b) an organic compound having a melting point of 30 to 100 ° C. (hereinafter referred to as component (b)). The present invention relates to a wrinkle removing agent composition for textiles used for heat treatment of textiles by a heat dryer.

  In addition, the present invention provides a wrinkle for a textile product, which is used for a heat treatment of a textile product by a rotary heating dryer, wherein the wrinkle removing agent composition for the textile product of the present invention is carried on a flexible absorbent. It relates to a removal material.

  Moreover, this invention relates to the wrinkle removal method of a fiber product which heat-processes a fiber product with a rotary heating dryer in presence of the wrinkle removal material of the said fiber product of the said invention.

  ADVANTAGE OF THE INVENTION According to this invention, the wrinkle removal method and the wrinkle removal material which can provide the textile product the wrinkle removal method of the textiles which can be easily performed in a general household without requiring ironing, and this effect are obtained.

<(A) component>
In the present invention, (poly) glycerol-modified silicone (hereinafter referred to as component (a)) is used. As the component (a) that can be used, JP-A-9-71504, JP-A-10-316526,
, Can be used. In the present invention, from the viewpoint of the effect of removing wrinkles, at least one branched (poly) glycerol chain containing one or more branched glycerol groups represented by the following structural formula (1) is connected to the silicon atom of silicone via a linking group. Most preferred are linked branched (poly) glycerol-modified silicone compounds.

[In the formula, two oxygen atoms are the same or different, and the above structural formula (1), the following structural formula (2), (3) or (4)

A glycerol group or a glycidol group represented by ]

  In the present invention, the branched (poly) glycerol chain contains one or more branched glycerol groups represented by the structural formula (1) (hereinafter referred to as group (1)) as branching groups. The branched (poly) glycerol chain has a structure in which a group (1), b glycidol groups represented by structural formula (2) (hereinafter referred to as group (2)), c structural formula (3) And a glycerol group represented by d structural formula (4) (hereinafter referred to as group (4)) as a terminal group. Yes (where a is an integer of 1 or more, b and c are integers of 0 or more, and d is an integer of 2 or more)

  In the present invention, the number (a + b + c + d) of the groups (1), (2), (3) and (4) in the branched (poly) glycerol chain is 3 or more. The number average number of bonds of the groups (1), (2), (3) and (4) in the branched (poly) glycerol chain determined by molecular weight comparison is preferably from 3 to 200, preferably from 3 to 100. More preferably, it is particularly preferably 3-50.

  In the branched (poly) glycerol chain, a / (a + b + c + d) is preferably 1/10 to 1/2, and more preferably 1/5 to 1/2, in order to have a sufficient adsorption effect.

  In the branched (poly) glycerol chain, the groups (1), (2), (3) and (4) may be optionally bonded.

  The linking group that bonds the silicon atom of silicone and the aforementioned branched (poly) glycerol chain is preferably a divalent group having an ether group or an ester group.

  The divalent group having an ether group is preferably a group represented by the general formula (5) (hereinafter referred to as a linking group (5)).

In the linking group (5), (R ^5a ) _e is bonded to a silicon atom, and (AO) _f is bonded to a branched (poly) glycerol chain.

-( ^R5a ) _e- O- (AO) _f- (5)
(In the formula, R ^5a may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms, and AO has 1 carbon atom. -4 alkyleneoxy group or C6-C10 aryleneoxy group, e is the number of 0 or 1, f is the number of 0-30, and f FO may be the same or different.)

The divalent group having an ester group is preferably a group represented by the general formula (6) (hereinafter referred to as a linking group (6)). In the linking group (6), R ^6a is bonded to a silicon atom, and (AO) _g is bonded to a branched (poly) glycerol chain.

—R ^6a —COO— (AO) _g — (6)
(In the formula, R ^6a may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms, and g is 0 to 30. And AO represents the above meaning, and g AOs may be the same or different.)

In the linking groups (5) and (6), the arylene group in R ^5a and R ^6a includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. R ^5a and R ^6a are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12, and methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene. , Octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like.

  e is preferably 1. As for f and g, 0-15 are preferable and 0-8 are still more preferable. The f AOs and the g AOs may be the same or different, and may be combined in a random or block form. An ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group is preferred.

As substituents in R ^5a and R ^6a , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group ( C1-C22) etc. are mentioned.

  The silicone forming the branched (poly) glycerol-modified silicone of the present invention is derived from polysiloxane, and the shape of the polysiloxane may be any of a chain, a branched chain, and a ring. The number average molecular weight of the polysiloxane is preferably 300 to 500,000, more preferably 300 to 100,000, and still more preferably 500 to 50,000. A number average molecular weight can be calculated | required with the measuring method mentioned later.

  Specific examples of these polysiloxanes include, for example, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,1,3,5. , 7,7,7-octamethyltetrasiloxane, tris (trimethylsiloxy) silane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5- Heptamethyltrisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,1,3,3,5,5 -Heptamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and the like.

  The branched (poly) glycerol-modified silicone of the present invention is preferably a silicone represented by the general formula (7) (hereinafter referred to as silicone (7)).

(Wherein R ^7a , R ^7b , R ^7c , h R ^7d , h R ^7e , R ^7f , R ^7g , and R ^7h are the same or different and linked with a branched (poly) glycerol chain) A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, which may have a group or a substituent, and may be substituted with a fluorine atom, or 6 to 22 carbon atoms Represents an aryl group, and at least one of R ^7a , R ^7b , R ^7c , h R ^7d , h R ^7e , R ^7f , R ^7g , R ^7h is a linked (poly) glycerol chain linked H represents a number from 0 to 10,000.)

In silicone (7), R ^7a , R ^7b , R ^7c , h R ^7d , h R ^7e , R ^7f , R ^7g , R ^7h other than the linking group to which the branched (poly) glycerol chain is bonded The groups may be the same or different and may have a substituent and may be substituted with a fluorine atom, a linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or It is an aryl group having 6 to 22 carbon atoms. Examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl, and the like. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxyl, ethoxyl, propoxyl, butoxyl, pentyloxyl, hexyloxyl, heptyloxyl, octyloxyl, nonyloxyl group, A trifluoroethoxy group etc. are mentioned. In addition, examples of the substituent include a hydroxy group, a carboxy group, an amino group, an imino group, a mercapto group, and an epoxy group. In these, a C1-C12 linear or branched alkyl group or alkenyl group, or a C6-C12 aryl group is preferable, and a C1-C3 alkyl group is still more preferable.

In the silicone (7), at least one of R ^7a , R ^7b , R ^7c , h R ^7d , h R ^7e , R ^7f , R ^7g , R ^7h , preferably 1 to 5, more preferably 1 to 3 are linking groups to which branched (poly) glycerol chains are bonded, and may be bonded to any position of silicone (7).

  H in silicone (7) represents a number of 0 to 10,000, preferably a number of 1 to 1,000, more preferably a number of 1 to 500.

  The number average molecular weight of the branched (poly) glycerol-modified silicone of the present invention is preferably 1000 to 500,000, more preferably 1000 to 200,000, and particularly preferably 1000 to 100,000. The method for measuring the number average molecular weight is based on GPC (polystyrene or polyethylene glycol equivalent) as described later.

  The branched (poly) glycerol-modified silicone of the present invention has a total number of silicon atoms (Si) in the silicone and groups (1), (2), (3) and (4) in the branched (poly) glycerol chain ( The ratio (G / Si) of (G) (hereinafter referred to as the number of glycerol groups) is preferably 0.1 to 10, more preferably 0.2 to 3, and particularly preferably 0.3 to 1.2. Within this range, it has an excellent wrinkle removal effect.

  The branched (poly) glycerol-modified silicone of the present invention is a silicone having one or more functional groups selected from the group consisting of a hydroxy group, a carboxy group, an amino group, an imino group, a mercapto group, and an epoxy group (hereinafter referred to as a precursor silicone). And 2,3-epoxy-1-propanol (hereinafter referred to as glycidol) in the presence of an acidic or basic catalyst.

  Examples of the precursor silicone include a silicone having a hydroxy group in which a group represented by the formula (8) is bonded to a silicon atom of silicone, a silicone having a carboxy group to which a group represented by the formula (9) is bonded, and a formula (10 ), A silicone having an amino group or an imino group to which a group represented by formula (II) is bonded, a silicone having a mercapto group to which a group represented by formula (11) is bonded, or a group represented by formula (12) or (13). A silicone having a bonded epoxy group is preferred. As the positions of these functional groups, any of the side chain of the silicone chain, both terminals and one terminal can be used. From the viewpoint of ease of reaction initiation, those having a hydroxy group or an epoxy group as the functional group are preferred.

-( ^R5a ) _e- O- (AO) _f- H (8)
(In the formula, R ^5a , e, f and AO have the above-mentioned meanings.)

_{^{-R 6a -COO- (AO) g -G}} 1 (9)
(Wherein R ^6a , g and AO have the above-mentioned meanings. G ¹ is a hydrogen atom, or metal, ammonium, alkyl having 1 to 22 carbon atoms or alkenyl ammonium, alkyl having 1 to 22 carbon atoms or alkenyl substitution. A group that forms a salt of pyridinium, an alkanol ammonium having 1 to 22 carbon atoms, or a basic amino acid.)

(In the formula, R ^10a represents a linear or branched alkylene group or alkenylene group having 1 to 22 carbon atoms, or an arylene group having 6 to 22 carbon atoms, and B and D are the same or different, and represent a hydrogen atom or a hydroxyl group. 1 represents an optionally substituted hydrocarbon group having 1 to 22 carbon atoms or an aminoalkyl group having 1 to 22 carbon atoms which may have a hydroxyl group, provided that at least one of X and Y represents hydrogen. Atom or an aminoalkyl group having a hydrogen atom in the amino group.)

-( ^R5a ) _e -S- (AO) _f- H (11)
(In the formula, R ^5a , e, f and AO have the above-mentioned meanings.)

  In the silicone having a hydroxy group, f in the formula (8) may be a large number of 10 or more in order to improve hydrophilicity, but the feature of the branched (poly) glycerol-modified silicone of the present invention is effectively used. In order to exhibit it, f is preferably 10 or less, more preferably 3 or less, and still more preferably 0 or 1.

  Silicone having a carboxy group is a compound in which a silicon atom and a carboxy group are bonded with a saturated hydrocarbon, or a carboxy group or a salt thereof is an imino group as described in Japanese Patent Application No. 2000-305741. Or the silicone couple | bonded with the silicon atom through the alkylene group which has an ether group as a substituent is preferable.

In the silicone having an amino group or imino group, R ^10a in formula (10) is preferably an alkylene group having 1 to 12 carbon atoms, such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexa Examples include methylene, heptamethylene and octamethylene groups.

  Specific examples of the group represented by the formula (10) include 3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (2-dimethylaminoethyl) -3-aminopropyl. Group, N-alkyl (C1-22) aminopropyl group and the like. Of these, a 3-aminopropyl group, an N- (2-aminoethyl) -3-aminopropyl group, an N- (2-dimethylaminoethyl) -3-aminopropyl group, particularly a 3-aminopropyl group is preferable.

The amine equivalent of the silicone having an amino group or imino group is preferably from 300 to 50,000 g / mol, more preferably from 300 to 10,000 g / mol, still more preferably from 300 to 5,000 g / mol, from the viewpoints of modification rate and reaction efficiency. It is. Further, since the reaction efficiency, the viscosity at 25 ° C., preferably from 10 to 1,000,000 mm ² / s, more preferably 20~10,000 mm ² / s. Viscosity, when the viscosity of the sample (25 ° C.) of less than 100,000 mm ² / s, measured with a B type viscometer, E-type viscosity when the viscosity of the measurement sample (25 ° C.) is more than 100,000 mm ² / s Measure with a meter.

In the silicone having a mercapto group or an epoxy group, R ^5a in formulas (11) and (12) is preferably an alkylene group having 1 to 12 carbon atoms, such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentane. Examples include methylene, hexamethylene, heptamethylene and octamethylene groups. In particular, a methylene group is preferable. e is 1 or 0, and 1 is preferable. f is 0 or 1, and 0 is preferable. Moreover, i in Formula (13) is preferably a number of 1 to 12.

Examples of the acidic catalyst used for the reaction between the precursor silicone and glycidol include Lewis acids such as HPF ₆ · Et ₂ O, SnCl ₄ , H ₂ SO ₄ , PhCOSbF ₆ , perchloric acid, fluorosulfuric acid, and trifluoromethanesulfonic acid. (Where Et represents an ethyl group and Ph represents a phenyl group).

  The amount of these acidic catalysts is 0 with respect to the total equivalent moles of functional groups such as hydroxy group, carboxy group, amino group, imino group, mercapto group, and epoxy group of the precursor silicone from the viewpoint that side reactions can be suppressed. 0.01 to 2 molar equivalents are preferred, and 0.1 to 1.0 molar equivalents are more preferred.

The basic catalyst used for the reaction between the precursor silicone and glycidol includes metal hydroxides such as NaOH, KOH, LiOH and CsOH, simple metals such as Na, K, Li and Cs, and a general formula ROM ² (R: alkyl) group, preferably an alkyl group having 1 to 12 carbon atoms, M ^2: metal alcoholates represented by an alkali metal), a metal hydride such as an alkali metal or alkaline earth metal. Of these, simple metals, metal hydroxides, and metal alcoholates are preferred because of their high activity.

  Since the amount of these basic catalysts can suppress side reactions, the total equivalent moles of functional groups such as hydroxy group, carboxy group, amino group, imino group, mercapto group, and epoxy group of the precursor silicone are as follows. 0.01-2 molar equivalent is preferable, and 0.1-1.0 molar equivalent is still more preferable.

  Examples of the side reaction include a cyclization reaction of glycidol and a formation reaction of a polymer of glycidol that does not bind to silicone.

  The basic catalyst is mixed with the precursor silicone in a solvent or without a solvent. As a solvent, a bipolar solvent such as tetrahydrofuran (THF); aliphatic hydrocarbons such as hexane, heptane, dodecane, cyclohexane, methylcyclohexane, isooctane, hydrogenated triisobutylene, and aromatic carbonization such as benzene, toluene, xylene, and ethylbenzene Examples thereof include hydrocarbon solvents such as hydrogen; silicone solvents such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. When using a solvent, the solvent is preferably used in an amount of 1 to 1000 parts by mass with respect to 1 part by mass of the catalyst.

  Among the basic catalysts, when a metal hydroxide or a metal alcoholate is used, it is preferable to perform dehydration or dealcoholization, for example, under reduced pressure after addition to the precursor silicone. Since water and / or alcohol causes the side reaction, it is preferable to reduce the abundance as much as possible. Next, preferably at 30 to 120 ° C., glycidol is added dropwise or intermittently while stirring. The dropping time depends on the dropping amount, but is preferably added for 0.5 to 24 hours, more preferably 1 to 12 hours. Glycidol may be diluted with a bipolar solvent such as THF and added. If necessary, after aging at the same temperature, cool.

  The amount of glycidol added is preferably 0.01 to 50 molar equivalents, more preferably 0.05 to 10 molar equivalents, relative to the precursor silicone.

<(B) component>
The component (b) of the present invention is an organic compound having a melting point of 30 to 100 ° C. Specifically preferred components (b) include (1) a fatty acid having 12 to 28 carbon atoms, (2) an alkylene (2 or 3 carbon) oxide adduct of oils and fats, and (3) an alkylene group having 2 or 2 carbon atoms. 3 is a polyalkylene glycol having a weight average molecular weight (determined from polyethylene glycol as a standard by gel permeation chromatography) of 1,000 to 15,000, and (4) an alkyl group having 10 to 18 carbon atoms, and an average addition mole A polyoxyethylene alkyl ether having 20 to 200 carbon atoms, or an ester compound of a fatty acid having 12 to 18 carbon atoms and a polyoxyalkylene having an average addition mole number of 20 to 200, (5) 3 hydroxy groups having 3 to 8 carbon atoms ~ 6 ester compounds of polyhydric alcohols and fatty acids having 10 to 20 carbon atoms (excluding the compound of (2)), or It may be mentioned those of alkylene (carbon number 2 or 3) oxide adducts.

  As the compound (1), capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid are preferable. As the compound (2), an ethylene oxide adduct of cured or semi-cured beef tallow or cured or semi-cured palm oil is suitable. As the compound (3), polyethylene glycol having a weight average molecular weight of 2,000 to 15,000 is suitable. As a compound of (4), carbon number of alkyl group is 12-18, polyoxyethylene alkyl ether having an average addition mole number of 55-200, and saturated fatty acid having 12-18 carbon atoms and average addition mole number of 55-200. Of these, ester compounds with polyoxyethylene are preferred. The polyhydric alcohol of the compound of (5) includes pentaerythritol, trimethylolpropane, and reducing sugars selected from apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose, xylose, sorbitan, sorbitol , Isosorbite and sorbite are preferable, and lauric acid, myristic acid, palmitic acid and stearic acid are preferable as the fatty acid. In the present invention, an ester of a polyhydric alcohol selected from sorbitan, sorbitol, isosorbite, and sorbite and a fatty acid selected from lauric acid, myristic acid, palmitic acid, and stearic acid is particularly preferable. Further, for the purpose of adjusting the melting point, it is also possible to use a compound obtained by further adding 1 to 30 mol of ethylene oxide thereto.

  In the present invention, the compound (4) and the compound (5) are particularly preferable, and the compound (5) is most preferable.

  By blending a component that is solid at room temperature such as component (b), it is possible to impart formability to the fiber product, and furthermore, as with component (a), the slippage between yarns of the fiber product is improved. The wrinkle removal effect can be enhanced. In addition, the component (b) also has an effect of suppressing static electricity generated when a textile product is processed with a rotary heat dryer.

  The wrinkle remover composition of the present invention is a wrinkle remover composition for a textile product, which contains the components (a) and (b) and is used for the heat treatment of the textile product by a rotary heat dryer. Various forms can be adopted depending on the method of use. Specifically, (i) the wrinkle removing agent is added to the rinsing water at the rinsing stage in the washing process of the textile product, and the treated textile product, which has been dehydrated after treating the textile product, is put into a rotary heating dryer and subjected to heat treatment. Method, (ii) a method in which a fiber product is sprayed using a sprayer such as a trigger container and then subjected to heat treatment in a rotary heat dryer, and (iii) a wrinkle obtained by impregnating the flexible absorbent with the composition. A method of performing a heat treatment in a rotary heat dryer together with a fiber product to be treated with a remover can be mentioned, and in particular, the method (iii) can impart an excellent wrinkle removing effect to the fiber product. preferable. The composition and method of the present invention are suitably applied to clothing, particularly among textile products. Details will be described below.

  When used in the method (i) and the method (ii), the composition of the present invention is in the form of a solution in which the component (a) and the component (b) are dissolved or dispersed in water and / or a water-soluble solvent. Preferably, the sum of component (a) and component (b) is preferably 0.1 to 70% by weight, more preferably 1.0 to 50% by weight, particularly preferably 2.0 to 40% by weight in the case of method (i), In the case of the method (ii), it is preferably 0.01 to 30% by mass, more preferably 0.02 to 20% by mass, and particularly preferably 0.05 to 15% by mass. The component (a) / component (b) is preferably 0.1 to 3, more preferably 0.3 to 2, particularly preferably 0.3 to 1.5 in terms of mass ratio. The pH (20 ° C.) of the composition is preferably from 3 to 10, more preferably from 4 to 9, from the viewpoint of storage stability. As a method for preparing such pH, ordinary sulfuric acid, hydrochloric acid, phosphorous Acids such as acid, citric acid and succinic acid and alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate can be used.

  In addition, it is preferable to use a surfactant for the purpose of stably dissolving or dispersing the component (a) and the component (b) in the solution, and the content is preferably 0.01 to 7% by mass, more preferably 0.01 to 5% by mass. It is. As the surfactant that can be used, alkylbenzenesulfonic acid having an alkyl group having 10 to 15 carbon atoms or a salt thereof, an alkyl sulfate salt having 10 to 16 carbon atoms, an alkyl group having 10 to 16 carbon atoms, Anionic surfactant selected from polyoxyethylene alkyl ether sulfate esters having an average addition mole number of 1 to 6, polyoxyethylene alkyl ether having an alkyl group having 10 to 16 carbon atoms and an average addition mole number of 4 to 20 A nonionic surfactant selected from alkyl polyglucosides having an alkyl group having 8 to 16 carbon atoms and an average degree of condensation of 1 to 5, one or two alkyl groups having 12 to 20 carbon atoms or alkenyl in the molecule Tetraalkyl type quaternary ammonium surfactants in which the remaining group is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Rukoto can.

  Examples of the solvent for dissolving or dispersing the component (a) and the component (b) include water and / or a water-soluble solvent. Examples of the water-soluble solvent include ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, and glycerin. Are preferred, and ethanol, ethylene glycol and / or propylene glycol are particularly preferred. Such a solvent is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, and particularly preferably 5 to 20% by mass in the composition.

  When the method (i) is employed in the present invention, the composition of the present invention is preferably rinsed in a quantity of 10 to 200 ml, more preferably 10 to 100 ml, particularly preferably 10 to 70 ml per kg of clothing. It is preferable to add from the viewpoint of wrinkle removing effect, and in particular, the component (a) is preferably 0.1 to 40 g, more preferably 0.5 to 20 g, particularly preferably 0.7 to 10 g, and the component (b) is 1 kg of clothing. It is preferable to add to rinse water so that the amount is preferably 0.2 to 70 g, more preferably 0.5 to 40 g, and particularly preferably 1.0 to 20 g.

  As the sprayer that can be used in the method (ii), a trigger sprayer is preferable, and 0.1 g to 2.0 g, preferably 0.2 to 1.5 g, more preferably 0.3 g to one stroke. What ejects 1.0 g is good. As the trigger type spray container used in the present invention, a pressure accumulation type trigger as disclosed in Japanese Utility Model Publication No. 4-37554 is particularly preferable in terms of spray uniformity.

As a spraying characteristic, a trigger type sprayer in which the area where the liquid is applied when spraying from a place 15 cm away onto an object placed vertically on the ground is 100 to 800 cm ² , preferably 150 to 600 cm ² is preferable.

  When the method (ii) is employed in the present invention, the composition of the present invention is preferably sprayed onto clothing so that the amount is preferably 50 to 900 ml, more preferably 60 to 700 ml, and particularly preferably 70 to 600 ml per 1 kg of clothing. It is suitable from the point of wrinkle removal effect, and (a) component is preferably 0.1 to 15 g per kg of clothing, more preferably 0.5 to 10 g, particularly preferably 0.7 to 5 g, and (b) component per kg of clothing. It is preferable to spray the clothes so that the amount is preferably 0.2 to 15 g, more preferably 0.5 to 10 g, and particularly preferably 1.0 to 7 g.

  When the method (i) is adopted, after adding the wrinkle removing agent composition at the rinsing stage, it can be dehydrated and wrinkled can be removed by performing heat treatment in a rotary heat dryer, In the method (ii), after the rinsing / dehydration is completed, the wet textile product is sprayed and then subjected to a heat treatment in a rotary heating dryer, and the dried textile product is sprayed on the wrinkled portion. Then, a method in which the heat treatment is performed again in the rotary heating dryer is suitable. In any case, the heat treatment temperature is preferably 40 to 120 ° C., more preferably 50 to 100 ° C., and the heat treatment time is preferably 5 to 120 minutes, more preferably 10 to 90 minutes.

  When the wrinkle removing composition of the present invention is used in the method (iii), in the presence of a wrinkle removing material in which a composition containing the component (a) and the component (b) is supported on a flexible absorbent. A method of heat-treating the fiber product in a rotary heat dryer is preferable. The wrinkle removing composition of the present invention to be used in the method (iii) is preferably a total of component (a) and component (b), preferably 0.05 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably Is 3 to 15% by mass, and the component (a) / component (b) is preferably 0.1 to 3, more preferably 0.3 to 2, particularly preferably 0.3 to 1.5 by mass ratio.

  In addition, it is preferable to contain water in the wrinkle removing composition provided for the method (iii) in order to effectively remove wrinkles, and the water content is preferably 40 to 99% by mass, more Preferably it is 50-99 mass%, Most preferably, it is 60-99 mass%. Further, water / [(a) component + (b) component] is preferably 1 to 20, more preferably 3 to 15, and particularly preferably 5 to 15. Further, when water is contained, the pH of the composition is preferably 3 to 10, more preferably 4 to 9, from the viewpoint of storage stability. Acids such as hydrochloric acid, phosphoric acid, citric acid and succinic acid and alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate can be used.

Examples of the flexible absorbent include paper, woven fabric, non-woven fabric, and sponge, and those having a porosity of 30 to 90% are particularly preferable. Here, the porosity can be obtained by the following equation.
Porosity = [1-W / (T × ε)] × 100
[W is the mass (g) of the flexible absorbent, T is the apparent volume (cm ³ ) of the flexible absorbent, and ε is the specific gravity of the material constituting the flexible absorbent. Show. ]

In the present invention, in particular, a nonwoven fabric is most suitable from the viewpoint of a wrinkle removing effect. Examples of the nonwoven fabric include spunlace, spunbond, meltblown, needle punch and / or stitchbond, in addition to dry nonwoven fabric such as wet nonwoven fabric, chemical bond, thermal bond, air lay, etc., particularly wet nonwoven fabric, chemical bond, One or more selected from thermal bonds, meltblowns, or spunlaces are preferred in terms of wrinkle removal effects. The nonwoven fabric preferably has a basis weight of 10 to 300 g / m ² , more preferably 10 to 200 g / m ² , and particularly preferably 15 to 180 g / m ² .

  As the material for the nonwoven fabric, a hydrophobic fiber selected from polypropylene, polyethylene, polyester, and polyvinyl chloride, and a hydrophilic fiber selected from nylon, rayon, acrylic, vinylon, polyurethane, and cellulose can be used. In the present invention, hydrophobic fibers and hydrophilic fibers can be used in combination.

  The flexible absorbent body of the present invention may be block-shaped or sheet-shaped, but a sheet-shaped one is preferable from the viewpoint of wrinkle removal effect. The average thickness of the sheet is preferably 50 μm to 3000 μm, and particularly preferably 100 μm to 2000 μm. Depending on the size of the rotary heat dryer, a sheet having a length of about 10 to 30 cm and a width of about 10 to 50 cm is suitable. It is.

When a flexible absorbent is used in the form of a sheet, the amount of the wrinkle removing composition supported is preferably 30 to 800 g / m ² , more preferably 50 to 600 g / m ² , and particularly preferably 100 to 500 g. / M ² is preferred. Supporting methods include reverse roll coater method, gravure roll coater method, opposite knife coater method, inverse knife coater method, kiss roll coater method, spray coat method, air knife coater method, dip roll coater method, direct roll coater method, brush coating method The dip roll coater method is particularly preferred from the viewpoint of ease of production.

In the method (iii), the fiber product is heat-treated with a rotary heat dryer in the presence of the fiber product wrinkle removing material of the present invention. The wrinkle removing agent composition for the textile product is preferably 10 to 200 g, more preferably 20 to 100 g, particularly preferably 30 to 90 g per kg of clothing from the viewpoint of the wrinkle removing effect. The component (a) is preferably 0.1 to 15 g per kg of clothing, more preferably 0.5 to 10 g, and the component (b) is preferably 0.2 to 15 g per kg of clothing, more preferably 0.5 to 10 g. Further, the amount of the textile product is preferably as small as possible with respect to the volume of the drying chamber of the rotary heat dryer, and it is preferable that the amount of the fiber product is 30 g / m ³ or less. The temperature of the rotary heat dryer treatment is preferably 40 to 120 ° C, more preferably 50 to 100 ° C, and the treatment time is preferably 5 to 120 minutes, more preferably 10 to 90 minutes.

<Synthesis Example 1> Synthesis of (a-1) (Branched Polyglycerol Modified Silicone A) GE Toshiba Silicone Co., Ltd. Carbinol Modified Silicone XF42-B0970 (both ends modified, hydroxyl group equivalent = 60 mg-KOH / g (average molecular weight) = 1870 equivalent)) 187 g was placed in a flask, 42.1 g of potassium methoxide (30% methanol solution) was added, and the mixture was heated to 60 ° C. under reduced pressure while stirring to distill off all of the methanol. As a result, potassium carbinol-modified silicone was obtained. The temperature was raised to 95 ° C., and 74.1 g (5 equivalents) of glycidol was added over 5 hours under a stream of argon with vigorous stirring using a metered liquid feed pump. After further heating and stirring for 20 minutes, the mixture was allowed to cool to room temperature, and 600 mL of ethanol was added to obtain a pale yellow solution. To this was added / stirred 34.6 g of citric acid, and the precipitated salt was filtered off. The filtrate was concentrated (removed if a small amount of polyglycerol derivative was precipitated) to obtain branched polyglycerol-modified silicone A as a pale yellow oil. Yield 95%. The ¹ H-NMR spectrum (methanol-d ₄ solution) of this branched polyglycerol-modified silicone A is shown in FIG. 1, and the ¹³ C-NMR spectrum (methanol-d ₄ solution) is shown in FIG. The assignment of each peak in the ¹ H-NMR spectrum and the assignment of the peak derived from the methine carbon of the group (1) in the ¹³ C-NMR spectrum are shown below. This branched polyglycerol-modified silicone A has —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ O— as a linking group.
¹ H-NMR spectrum
0.1-0.2ppm (Si-CH ₃₎
0.6-0.7ppm (4H, Si-CH ₂ -CH _2- )
1.6-1.8ppm (4H, Si-CH ₂ -CH _2- )
_{3.3-4.0ppm (12H, Si-CH 2} -CH 2 -CH 2 -O-CH 2 -CH 2 -O, branched (poly) H of glycerol chain)
¹³ C-NMR spectrum

By analysis of ¹³ C-NMR spectrum, it was confirmed to be a branched polyglycerol-modified silicone having group (1). Further, by analysis of ¹ H-NMR spectrum, average number of glycerol groups (G) = 9.8 (one side 4.9), average number of silicon atoms (Si) = 22. The G / Si ratio is 0.45, and according to GPC analysis (column: KF-804L (× 2), aliphatic amine / chloroform solution, 40 ° C., polystyrene conversion), the number average molecular weight (Mn) is 2600.

<Synthesis Example 2> Synthesis of (a-2) (branched polyglycerol-modified silicone B) Carbinol-modified silicone KF-6001 (both ends modified, hydroxyl equivalent = 62 mg-KOH / g (average molecular weight) manufactured by Shin-Etsu Chemical Co., Ltd. = 1810 equivalent)) 181 g was placed in a flask, 46.7 g of potassium methoxide (30% methanol solution) was added, and the mixture was heated to 60 ° C. under reduced pressure to distill off all the methanol. Potassium carbinol-modified silicone was obtained as a slightly yellow oil. The temperature was raised to 95 ° C., and 177.8 g (12 equivalents) of glycidol was added over 8 hours under a stream of argon with vigorous stirring using a metering liquid feed pump. After further heating and stirring for 20 minutes, the mixture was allowed to cool to room temperature to obtain an emulsion paste composition. After adding 800 mL of ethanol and removing potassium with a cation exchange resin, the solution was concentrated (removed if a small amount of polyglycerol derivative is precipitated here) to obtain branched polyglycerol-modified silicone B as a slightly yellow viscous oil. Yield 92%. By analysis of ¹³ C-NMR spectrum, it was confirmed to be a branched polyglycerol-modified silicone having group (1). Further, by analysis of ¹ H-NMR spectrum, average number of glycerol groups (G) = 23.6 (one side 11.8), average number of silicon atoms (Si) = 22. The G / Si ratio was 1.07, and the number average molecular weight (Mn) was 3590 according to GPC analysis (column: G4000PWXL + G2500PWXL, acetonitrile / phosphate buffer, 40 ° C., polyethylene glycol equivalent). . The branched polyglycerol-modified silicone B has —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ O— as a linking group.

<Synthesis Example 3> Synthesis of (a-3) (branched polyglycerol-modified silicone C) Carbinol-modified silicone KF-6003 (both end-modified, hydroxyl group equivalent = 22 mg-KOH / g (average molecular weight) manufactured by Shin-Etsu Chemical Co., Ltd. = Equivalent to 5100)) 255 g was placed in a flask, purged with argon, added with 3.13 g of shredded potassium, and stirred at 60 ° C. until the piece of potassium disappeared to obtain a potassiumated carbinol-modified silicone as an oil. . The temperature was raised to 95 ° C., and 29.6 g (4 equivalents) of glycidol was added over 5 hours under a stream of argon with vigorous stirring. After further heating and stirring for 20 minutes, the mixture was allowed to cool to room temperature, and 600 mL of ethanol was added to obtain a pale yellow solution. To this was added / stirred 15.4 g of citric acid, and the precipitated salt was filtered off. The filtrate was concentrated (removed if a small amount of polyglycerol derivative is precipitated) to obtain branched polyglycerol-modified silicone C as a colorless oil. Yield 88%. By analysis of ¹³ C-NMR spectrum, it was confirmed to be a branched polyglycerol-modified silicone having group (1). Further, by analysis of ¹ H-NMR spectrum, average number of glycerol groups (G) = 15.9 (one side 8.0), average number of silicon atoms (Si) = 69. The G / Si ratio is 0.23, and the result of GPC (solvent chloroform) of this branched polyglycerol-modified silicone C is shown in FIG. According to GPC analysis (column: KF-804L (× 2), aliphatic amine / chloroform solution, 40 ° C., polystyrene conversion), the number average molecular weight (Mn) was 6280. The branched polyglycerol-modified silicone C has —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ O— as a linking group.

<Example 1>
[1] Wrinkle remover composition Wrinkle remover compositions having the compositions shown in Table 1 were prepared. The following were used as the components (a) and (b). Moreover, pH (20 degreeC) of the composition was adjusted with 0.1N sulfuric acid aqueous solution and 0.1N sodium hydroxide aqueous solution.

(A-1): Branched polyglycerol-modified silicone A produced in Synthesis Example 1
(A-2): Branched polyglycerol-modified silicone B produced in Synthesis Example 2
(A-3): Branched polyglycerol-modified silicone C produced in Synthesis Example 3
(A-4): SH-200 dimethyl silicone oil, manufactured by Toray Dow Corning Co., Ltd., comparative component (a-5): FZ-2166 polyether-modified silicone, manufactured by Nihon Unicar Co., Ltd., comparative component (b-1) sorbitan mono Stearate (Brand name Leo Doll Super SP-S 10, Kao Corporation, melting point 52 ° C.)
(B-2) Stearyl alcohol (reagent, melting point 60 ° C.)
(B-3) Polyoxyethylene alkyl ether (trade name: Emulgen 220, manufactured by Kao Corporation, melting point: about 40 ° C.)

[2] Wrinkle remover After the wrinkle remover composition shown in Table 1 is melt-mixed at about 70 ° C., it is supported by a gravure roll coater method on a polyester nonwoven fabric having a porosity of 70%, a basis weight of 75 g / m ² and a thickness of about 700 μm. I let you. At that time, the loading was adjusted to 400 g / m ² . The sheet thus obtained was cut into a length of 30 cm and a width of 30 cm to obtain a wrinkle removal material for testing.

[3] Wrinkle removal method Fully automatic washing machine (NA-F50K1 Easy Aisuma No. Standard Course, made by Matsushita Electric Industrial Co., Ltd.) in advance using a commercially available Y-shirt (trade name: Shape-stable shirt ECOSYS 28 ° C polyester / cotton = 50/50) A wrinkle evaluation Y-shirt was washed 60 times using

  Using a rotary clothes dryer for home use (NH-D502 type, manufactured by Matsushita Electric Industrial Co., Ltd.), put three Y-shirts for wrinkle evaluation after hanging and drying and one test wrinkle remover. The dryer was run for 20 minutes. Under this condition, the mass of the wrinkle removing composition in the wrinkle removing material is about 5% with respect to the mass of the wrinkle evaluation Y-shirt.

  The Y-shirt treated with the dryer was removed from the dryer and allowed to stand at room temperature for 1 hour, and then the degree of wrinkle removal was determined. Judgment was made by 5 panelists based on the following criteria, and the average value was obtained as the evaluation score for the wrinkle level. The results are shown in Table 1. The wrinkle level evaluation score when the wrinkle removing material of the present invention is not used is 2.5.

"Wrinkle criteria"
5: No wrinkles 4: Little wrinkles 3: Slightly wrinkles remain 2: Wrinkles remain considerably 1: Wrinkles remain remarkably

<Example 2>
10% by mass of (a-1), 12% by mass of (b-1), 3% by mass of polyoxyethylene lauryl ether (oxyethylene group average condensation degree 8), 3% by mass of propylene glycol, and the remaining water ( A wrinkle removal composition containing 0.1 N sulfuric acid aqueous solution and 0.1 N sodium hydroxide aqueous solution is adjusted to a pH of 20 ° C. at 7.0). A commercially available Y-shirt (trade name: EOSSYS 28 ° C polyester / cotton = 50/50) was repeated 60 times in advance using a fully automatic washing machine (NA-F50K1 Easy Aisuma Standard Course, manufactured by Matsushita Electric Industrial Co., Ltd.). The laundry was used as a wrinkle evaluation Y-shirt. Five of these Y shirts and 40 g of the wrinkle removing composition were poured into a washing machine and stirred in 40 L of tap water for 5 minutes. Thereafter, the Y-shirt was dehydrated, and the dryer was operated for 60 minutes using a household rotary clothes dryer (NH-D502, manufactured by Matsushita Electric Industrial Co., Ltd.). The condition of wrinkles on the Y-shirt after drying is almost free of wrinkles in all Y-shirts.

<Example 3>
(A-2) 3% by mass, (b-1) 3% by mass, polyoxyethylene lauryl ether (oxyethylene group average condensation degree 8) 1.0% by mass, propylene glycol 3.0% by mass, A wrinkle removing composition containing the remaining water (pH adjusted at 20 ° C. to 7.0 with 0.1 N aqueous sulfuric acid solution and 0.1 N aqueous sodium hydroxide solution) is prepared. A commercially available Y-shirt (trade name: EOSSYS 28 ° C polyester / cotton = 50/50) was repeated 60 times in advance using a fully automatic washing machine (NA-F50K1 Easy Aisuma Standard Course, manufactured by Matsushita Electric Industrial Co., Ltd.). The laundry was used as a wrinkle evaluation Y-shirt. In the final washing, these Y-shirts were hung indoors and dried. 50 g (25% by mass with respect to the mass of the Y shirt) of the wrinkle remover composition was sprayed on one of these Y shirts (about 200 g) using a trigger container. Thereafter, using a household rotary clothes dryer (NH-D502 type, manufactured by Matsushita Electric Industrial Co., Ltd.), the dryer was operated for 60 minutes on five Y-shirts. The condition of wrinkles on the Y-shirt after drying is almost free of wrinkles in all Y-shirts.

2 is a ¹ H-NMR spectrum of branched polyglycerol-modified silicone A obtained in Example 1. FIG. 3 is a ¹³ C-NMR spectrum of branched polyglycerol-modified silicone A obtained in Example 1. FIG. FIG. 4 is a diagram showing the GPC results of branched polyglycerol-modified silicone C obtained in Example 3.

Claims (4)

A wrinkle removal composition for textiles, which is used for heat treatment of textiles by a rotary heat dryer, comprising (a) (poly) glycerol-modified silicone and (b) an organic compound having a melting point of 30 to 100 ° C. . (A) is a structure in which at least one branched (poly) glycerol chain containing at least one branched glycerol group represented by the following structural formula (1) is bonded to a silicon atom of silicone via a linking group ( The composition for removing wrinkles of textiles according to claim 1, which is a poly) glycerol-modified silicone.

[In the formula, two oxygen atoms are the same or different, and the above structural formula (1), the following structural formula (2), (3) or (4)

A glycerol group or a glycidol group represented by ] A wrinkle removal material for a textile product, which is used for heat treatment of a textile product by a rotary heating dryer, wherein the wrinkle removing agent composition for the textile product according to claim 1 or 2 is supported on a flexible absorbent body. A method for removing wrinkles from a textile product, wherein the textile product is heat-treated with a rotary heat dryer in the presence of the material for removing wrinkles from the textile product according to claim 3.

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